Aqueous coating compositions method for the production thereof and their use for producing in particular thixotropic coating compositions

ABSTRACT

The invention relates to aqueous coating agents containing binding agents and at least one aqueous plastic dispersion, based on one homopolymer and/or copolymer that is/are derived from α,β unsaturated compounds (M). Said coating agents also contain at least one protective colloid containing hydroxyl groups and comprising ethylenically unsaturated groups and optionally additional feed material that is conventionally used for producing coating agents. According to the invention, the protective colloid contains ethylenically unsaturated groups in a quantity that is expressed as the molar degree of substitution MS of unsaturated groups, R unsaturated , ranging between 0.001 and 1.0. The invention also relates to a method for producing said coating agents and to their use for producing thixotropic coating agents by the addition of thixotroping agents, in particular metal chelates.

Aqueous polymer dispersions have long been used on account in particularof their eco-friendly character for preparing aqueous coatingcompositions with binder which are suitable on the one hand as paintsfor decorating and protecting substrates and on the other hand asadhesives for joining substrates.

In the context of the use of paints it is very advantageous if thepaints are on the one hand of such high viscosity that they do not dripbut on the other hand can be induced to have a flow behavior for whichunevennesses, such as brush lines or brush furrows originating frombrush application, for example, have the opportunity to even out.Conditions are optimum when a paint which is pseudoplastic per seresponds to the attack of a shearing force by opposing the attackingforce with a resistance which grows as the shearing force increases andwhich when a certain shearing force—which ought not to be either toohigh or too low—is reached suddenly collapses, with the paint thendisplaying flow behavior which is typical for thixotropic paints, i.e.,time-dependent reduction in viscosity when the shear rate changes.Paints exhibiting such rheology do not drip from the applicator (e.g.,brush or lamb's wool roller) but under the shearing forces whichnormally arise in the course of processing become of such low viscositythat unevennesses, e.g., brush lines or brush furrows, are able largelyto flow out. Left at rest, the paint then regains a relatively highviscosity with sufficient rapidity that it is impossible for“curtaining” to develop when the paint is applied to vertical surfaces.Moreover, a paint having such rheology allows paint application in asingle operation in a substantially greater film thickness than ispossible in the case of paints having a more simple flow behavior. Inaddition it is possible for the user to work more quickly oreconomically, since when new paint is taken on each time the processingequipment is able to hold a larger quantity of paint, owing to theabsence of the tendency to drip, than with paints having conventionalflow properties.

In the case of aqueous formulations with binder which are used asadhesives as well it is possible for the thixotroping described to be ofadvantage. For example, thixotroped dispersions which function asadhesives are often much less prone toward sedimentation thannonthixotroped dispersions. In spite of this, thixotroped dispersions,in a manner similar to that for nonthixotroped dispersions, can bepumped or processed on high-speed machines, since the original, lowviscosity of the dispersion can easily be reestablished by shearing.

Within the field of alkyd resin paints there have long been thixotropicpaints which possess the aforementioned advantages, as a result of theaddition of polyamide resin, for example.

Thixotropic paints based on aqueous polymer dispersions are also known.In the case of such materials the thixotropy can be produced in thepaint by the incorporation of specific additives, such asmontmorrilonites or water glass, into the paint by mixing, for example.

DE-A-12 42 306 discloses a thixotropic coating material based on afilm-forming polymer, an organic polyhydroxy compound, and a titaniumchelate in aqueous medium, for which the film-forming polymer used is awater-emulsified homopolymer or copolymer of vinyl esters, acrylic andmethacrylic esters, styrene, acrylonitrile, and butadiene, thepolyhydroxy compound used is a natural or synthetic, water-soluble,hydroxyl-containing organic colloid, and from 0.2 to 5% by weight oftitanium chelate is used, based on the emulsion weight.

DE-A-26 20 189 describes thixotropic mixtures composed of a) one or moreaqueous polymer dispersions comprising a copolymer of α,β-unsaturatedcompounds which contains acetoacetate groups, b) a hydroxyl-containingprotective colloid, c) a heavy metal chelate, and d) other usualadditives.

Although these processes are superior to others described before them,they still have certain disadvantages. For example, when some titaniumchelates are used, it is common for yellowing phenomena to appear in thecoating, the propensity to yellow increasing with the amount of chelate.Additionally, many of the chelates are of very limited solubility inwater and, in particular at the point of dropwise introduction, theycause a low level of formation of coagulum, which in the case of glosspaints, for example, can have adverse effects on the gloss. Thecombination of a chelate with dispersions which comprisehydroxyl-containing protective colloids frequently also leads tothixotropic coating compositions having an unsatisfactory gel structure(gel strength). In order to achieve a sufficient gel strength it ispossible to resort to increasing either the amount of chelate or theamount of hydroxyl-containing protective colloid in the dispersion, orboth, but in that case it may be necessary to accept, with an increasingamount of chelate, a greater prevalence of disadvantages (yellowingpropensity, formation of coagulum at the point of dropwise introduction)or, with an increasing amount of protective colloid, it may be necessaryto accept greater prevalence of disadvantages (poor leveling propertieson account of increased viscosity, reduced water sensitivity of thepolymer film as a result of the higher fraction of hydroxyl-containingprotective colloid).

DE-A-197 08 531 and DE-A-197 51 712 describe the use of water-soluble,nonionic cellulose ethers from the group of the alkylcelluloses andhydroxyalkylcelluloses which are additionally substituted by butenyl and2-propenyl groups as protective colloids for emulsion polymerization.The examples specify the preparation of polymer dispersions with thesehydroxyl-containing protective colloids. Aqueous coating compositions,such as paints and/or adhesives, with binder that comprise these polymerdispersions, however, are not disclosed.

It was an object of the present invention, therefore, to provide aqueouscoating compositions with binder which can be used either as adhesivesor as paints and which exhibit the disadvantages described above eithernot at all or only to a small extent.

Another object of the present invention was to provide aqueous coatingcompositions with binder which following the addition of equal orsmaller amounts of metal chelates, in contrast to the known coatingcompositions, are distinguished by a markedly improved thixotropability(gel strength); it is intended that the preparation of the binder usedshould take place using equal or smaller amounts of hydroxyl-containingprotective colloid.

Surprisingly it has now been found that these objects are achieved bypreparing the binders used for the coating compositions of the inventionusing hydroxyl-containing protective colloids which containethylenically unsaturated radicals.

The present invention accordingly provides aqueous coating compositionswith binder, comprising

-   -   at least one aqueous polymer dispersion based on a homopolymer        and/or copolymer derived from α,β-unsaturated compounds (M)        which    -   comprises at least one hydroxyl-containing protective colloid        having ethylenically unsaturated radicals, and    -   if desired, further ingredients customary for the preparation of        coating materials.

The selection of the α,β-unsaturated compounds (M) suitable forpreparing the polymer dispersions is not critical per se. Suitabilityextends to all monomers usually used for preparing polymer dispersionsthat can be combined with one another rationally in accordance with therequirements of the art.

Preference as principal monomers (MP) is given to vinyl esters ofcarboxylic acids having 1 to 18 carbon atoms (MP1), esters and,respectively, monoesters of ethylenically unsaturated C₃-C₈monocarboxylic and dicarboxylic acids with C₁-C₁₈ alkanols (MP2),aromatic or aliphatic α,β-unsaturated, optionally halogen-substitutedhydrocarbons (MP3). As functional monomers (MF) it is possible to usenot only ionic monomers (MF1) but also nonionic monomers (MF2), and alsofurther ethylenically unsaturated monomers (MF3).

As vinyl esters of carboxylic acids having 1 to 18 carbon atoms (MP1) itis possible to use any of the monomers known to the skilled worker.Particular preference, however, is given to vinyl esters of carboxylicacids having 1 to 4 carbon atoms, such as vinyl formate, vinyl acetate,vinyl propionate, vinyl isobutyrate, vinyl pivalate, and vinyl2-ethylhexanoate, for example; vinyl esters of saturated, branchedmonocarboxylic acids having 9, 10 or 11 carbon atoms in the acid radical(®Versatic acids); vinyl esters of relatively long-chain saturated andunsaturated fatty acids, examples being vinyl esters of fatty acidshaving 8 to 18 carbon atoms, such as vinyl laurate and vinyl stearate,for example; and vinyl esters of benzoic acid or of p-tert-butylbenzoicacid and also mixtures thereof, such as mixtures of vinyl acetate and aVersatic acid or of vinyl acetate and vinyl laurate, for example.Particular preference is given to vinyl acetate.

As esters and, respectively, monoesters of ethylenically unsaturatedC₃-C₈ mono- and dicarboxylic acids with C₁-C₁₈ alkanols (MP2) it ispossible to use any of the monomers known to the skilled worker. Theesters and, respectively, monoesters of ethylenically unsaturated C₃-C₈monocarboxylic and dicarboxylic acids with C₁-C₁₂ alkanols arepreferred, with C₁-C₈ alkanols or C₅-C₈ cycloalkanols being particularlypreferred.

Suitable C₁-C₁₈ alkanols are for example methanol, ethanol, n-propanol,isopropanol, 1-butanol, 2-butanol, isobutanol, tert-butanol, n-hexanol,2-ethylhexanol, lauryl alcohol, and stearyl alcohol. Suitablecycloalkanols are for example cyclopentanol and cyclohexanol.Particularly preferred are the esters of acrylic acid, of (meth)acrylicacid, of crotonic acid, of maleic acid, of itaconic acid, of citraconicacid, and of fumaric acid. Especially preferred are the esters ofacrylic acid and/or of (meth)acrylic acid, such as, for example,methyl(meth)acrylate, ethyl(meth)acrylate, isopropyl (meth)acrylate,n-butyl(meth)acrylate, isobutyl(meth)acrylate, 1-hexyl (meth)acrylate,tert-butyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, and also theesters of fumaric acid and of maleic acid, such as, for example,dimethyl fumarate, dimethyl maelate, di-n-butyl maleate, di-n-octylmaleate, and di-2-ethylhexyl maleate. If desired it is also possible forsaid esters to be substituted by epoxy and/or hydroxyl groups.

Examples of aromatic or aliphatic α,β-unsaturated, optionallyhalogen-substituted hydrocarbons (MP3) are ethene, propene, 1-butene,2-butene, isobutene, styrene, vinyltoluene, vinyl chloride, andvinylidene chloride, with ethene and styrene being preferred.

By ethylenically unsaturated ionic monomers (MF1) are meant in thepresent specification preferably those ethylenically unsaturatedmonomers which have a water solubility of more than 50 g/l, preferablymore than 80 g/l, at 25° C. and 1 bar and which in dilute aqueoussolution at a pH of 2 and/or 11 are more than 50%, preferably more than80% in ionic compound form or else at a pH of 2 and/or 11 are more than50%, preferably more than 80%, transformed into an ionic compound byprotonation or deprotonation.

Suitable ethylenically unsaturated ionic monomers (MF1) are thosecompounds which carry at least one carboxylic acid, sulfonic acid,phosphoric acid or phosphonic acid group directly adjacent to the doublebond unit or else are joined to it via a spacer. Examples that may bementioned include the following: α,β-unsaturated C₃-C₈ monocarboxylicacids, α,β-unsaturated C₅-C₈ dicarboxylic acids and their anhydrides,and monoesters of α,β-unsaturated C₄-C₈ dicarboxylic acids.

Preference is given to unsaturated monocarboxylic acids, such as acrylicacid and (meth)acrylic acid and their anhydrides, for example;unsaturated dicarboxylic acids, such as maleic acid, fumaric acid,itaconic acid, and citraconic acid and their monoesters with C₁-C₁₂alkanols, such as monomethyl maleate and mono-n-butyl maleate, forexample. Further preferred ethylenically unsaturated ionic monomers MF1are ethylenically unsaturated sulfonic acids such as vinylsulfonic acid,2-acrylamido-2-methylpropanesulfonic acid, 2-acryloyloxyethanesulfonicacid, and 2-meth-acryloyloxyethanesulfonic acid, 3-acryloyloxy- and3-methacryloyl-oxypropanesulfonic acid, vinylbenzenesulfonic acid, andalso ethylenically unsaturated phosphonic acids, such as vinylphosphonicacid.

In addition, as well as the stated acids, it is also possible to usetheir salts, preferably their alkali metal or ammonium salts, and withparticular preference their sodium salts, such as the sodium salts ofvinylsulfonic acid and of 2-acrylamidopropanesulfonic acid, for example.

The ethylenically unsaturated free acids referred to, in aqueoussolution at a pH of 11, are predominantly in the form of their conjugatebases in anionic form and, like the stated salts, can be referred to asanionic monomers.

Also suitable as ethylenically unsaturated ionic monomers (MF1) aremonomers having cationic functionality, such as monomers deriving fromquaternary ammonium groups, for example. Preference, however, is givento anionic monomers.

By ethylenically unsaturated nonionic monomers (MF2) are meant in thepresent specification preferably those ethylenically unsaturatedcompounds which have a water solubility of more than 50 g/l, preferablymore than 80 g/l, at 25° C. and 1 bar and which in dilute aqueoussolution at a pH of 2 and at a pH of 11 are predominantly in nonionicform.

Preferred ethylenically unsaturated nonionic monomers (MF2) are not onlythe amides of the carboxylic acids specified in connection with theethylenically unsaturated ionic monomers (M3), such as (meth)acrylamideand acrylamide, for example, but also water-soluble N-vinyl lactams,such as N-vinylpyrrolidone, for example, and compounds which asethylenically unsaturated compounds contain covalently bondedpolyethylene glycol units, such as polyethylene glycol monoallyl ordiallyl ethers or the esters of ethylenically unsaturated carboxylicacids with polyalkylene glycols, for example.

Suitable further ethylenically unsaturated monomers (MF3) includemonomers containing siloxane groups, of the formula RSi(CH₃)₀₋₂(OR¹)₃₋₁,where R has the definitions CH₂═CR²—(CH₂)₀₋₁ or CH₂═CR²CO₂—(CH₂)₁₋₃, R¹is an unbranched or branched, optionally substituted alkyl radicalhaving 3 to 12 carbon atoms, which can if desired be interrupted by anether group, and R² is H or CH₃.

Preference is given to silanes of the formulaeCH₂═CR²—(CH₂)₀₋₁Si(CH₃)₀₋₁(OR¹)₃₋₂ andCH₂═CR²CO₂—(CH₂)₃Si(CH₃)₀₋₁(OR¹)₃₋₂, where R¹ is a branched orunbranched alkyl radical having 1 to 8 carbon atoms and R² is H or CH₃.

Particularly preferred silanes are vinylmethyldimethoxysilane,vinylmethyldiethoxysilane, vinylmethyldi-n-propoxysilane,vinylmethyldiiso-propoxysilane, vinylmethyldi-n-butoxysilane,vinylmethyldi-sec-butoxy-silane, vinylmethyldi-tert-butoxysilane,vinylmethyldi(2-methoxyisopropyl-oxy)silane, andvinylmethyldioctyloxysilane.

Particular preference is given to silanes of the formulaCH₂═CR²—(CH₂)₀₋₁Si(OR¹)₃ and CH₂═CR²CO₂—(CH₂)₃(OR¹)₃, where R¹ is abranched or unbranched alkyl radical having 1 to 4 carbon atoms and R²is H or CH₃. Examples thereof areγ-(meth)acryloyloxypropyltris(2-meth-oxyethoxy)silane,γ-(meth)acryloyloxypropyltrismethoxysilane,γ-(meth)-acryloyloxypropyltrisethoxysilane,γ-(meth)acryloyloxypropyltris-n-prop-oxysilane,γ-(meth)acryloyloxypropyltrisisopropoxysilane,γ-(meth)acryloyl-oxypropyltrisbutoxysilane,γ-acryloyloxypropyltris(2-methoxyethoxy)silane,γ-acryloyloxypropyltrismethoxysilane,γ-acryloyloxypropyltrisethoxysilane,γ-acryloyloxypropyltris-n-propoxysilane,γ-acryloyloxypropyltrisisopropoxy-silane,γ-acryloyloxypropyltrisbutoxysilane, and alsovinyltris(2-methoxy-ethoxy)silane, vinyltrismethoxysilane,vinyltrisethoxysilane, vinyltris-n-propoxysilane,vinyltrisisopropoxysilane and vinyltrisbutoxysilane. The stated silanecompounds can if desired also be used in the form of their (partial)hydrolysates.

Additionally suitable as further ethylenically unsaturated monomers(MF3) are nitriles of α,β-monoethylenically unsaturated C₃-C₈ carboxylicacids, such as acrylonitrile and (meth)acrylonitrile, for example, andalso adhesion-improving and crosslinking monomers. It is also possibleto use C₄-C₈ conjugated dienes, such as 1,3-butadiene, isoprene, andchloroprene, for example, as monomers (M6).

The adhesion-improving monomers include not only compounds which have anacetoacetoxy unit bonded covalently to the double bond system but alsocompounds having covalently bonded urea groups. The first-mentionedcompounds include in particular acetoacetoxy ethyl (meth)acrylate andallyl acetoacetate. The compounds containing urea groups include forexample N-vinylurea and N-allylurea and also derivatives ofimidazolidin-2-one, such as N-vinyl- and N-allylimidazolidin-2-one,N-vinyloxyethylimidazolidin-2-one,N-(2-(meth)acrylamidoethyl)-imidazolidin-2-one,N-(2-(meth)acryloyloxyethyl)imidazolidin-2-one,N-(2-(meth)acryloyloxyacetamidoethyl)imidazolidin-2-one, and also otheradhesion promoters known to the skilled worker and based on urea orimidazolidin-2-one. Additionally suitable for improving the adhesion isdiacetoneacrylamide in combination with the subsequent addition ofadipic dihydrazide to the dispersion. The adhesion-promoting monomerscan be used where appropriate in amounts of from 0.1 to 10% by weight,preferably from 0.5 to 5% by weight, based on the total amount of themonomers. Preferably, however, the copolymers do not contain any ofthese adhesion-promoting monomers in copolymerized form.

As crosslinking monomers it is possible to use not only difunctional butalso polyfunctional monomers. Examples thereof are diallyl phthalate,diallyl maleate, triallyl cyanurate, tetraallyloxyethane,divinylbenzene, butane-1,4-diol di(meth)acrylate, triethylene glycoldi(meth)acrylate, divinyl adipate, allyl(meth)acrylate, vinyl crotonate,methylenebisacrylamide, hexanediol diacrylate, pentaerythritoldiacrylate, and trimethylolpropane triacrylate. The crosslinkingmonomers can be used where appropriate in amounts of from 0.02 to 5% byweight, preferably from 0.02 to 1% by weight, based on the total amountof the monomers.

The selection of the suitable monomers or monomer combinations must takeaccount of the generally recognized considerations relating to thepreparation of dispersions which are used for preparing coatingmaterials. Thus in particular it should be ensured that polymers areformed which form a film under the envisaged drying conditions of thecoating, and that the selection of the monomers for preparing copolymersis made such that in accordance with the position of the polymerizationparameters the formation of copolymers can be expected. Some preferredmonomer combinations are listed below:

Preferred monomer mixtures from the monomers M for preparing copolymersare vinyl acetate/vinyl chloride/ethene, vinyl acetate/vinyllaurate/ethene, vinyl acetate/vinyl laurate/ethene/vinyl chloride, vinylacetate/Versatic acid vinyl ester/ethene/vinyl chloride, Versatic acidvinyl ester/ethene/vinyl chloride, vinyl acetate/Versatic acid vinylester/ethene, and vinyl acetate/ethene, particular preference beinggiven to the combination vinyl acetate/ethene. Further of preference arevinyl acetate/butyl acrylate, vinyl acetate/dibutyl maleate, vinylacetate/dibutyl fumarate, vinyl acetate/2-ethylhexyl acrylate, vinylacetate/ethene/butyl acrylate, vinyl acetate/ethene/dibutyl maleate,vinyl acetate/ethene/dibutyl fumarate, vinyl acetate/ethene/2-ethylhexylacrylate, methyl methacrylate/butyl acrylate, methylmethacrylate/2-ethylhexyl acrylate, styrene/butyl acrylate,styrene/2-ethylhexyl acrylate, methyl methacrylate/isobutyl acrylate,and methyl methacrylate/isopropyl acrylate.

Particular preference is given to monomer mixtures which include vinylesters, since they can be prepared more easily and with a greaterbreadth of variation in the presence of hydroxyl-containing protectivecolloids than can corresponding monomer mixtures which do not includeany vinyl ester components.

The dispersion used in accordance with the invention comprises at leastone protective colloid and if desired at least one emulsifier. Theprotective colloids are polymeric compounds, having molecular weights ofmore than 2000 g/mol for example, whereas the emulsifiers are lowmolecular weight compounds whose relative molecular weights are below2000 g/mol, for example.

The dispersion used in accordance with the invention compriseshydroxyl-containing protective colloids distinctive in that they containethylenically unsaturated radicals.

The amounts used of hydroxyl-containing protective colloid containingethylenically unsaturated radicals are 0.05-25% by weight, preferably0.1-20% by weight, more preferably 0.2-15% by weight, with particularpreference 0.3-10% by weight, and very preferably 0.4-5% by weight,based on the total mass of the monomers used to prepare the dispersion.

It is preferred to employ hydroxyl-containing protective colloids atleast some of whose hydroxyl groups are substituted by ethylenicallyunsaturated radicals.

Particular preference is given to hydroxyl-containing cellulose ethersat least some of whose hydroxyl groups are substituted by ethylenicallyunsaturated radicals. Cellulose ethers are obtainable, as is known, byetherification or alkylation of cellulose molecules. Cellulose moleculesare constructed of anhydroglucose units, there being in eachanhydroglucose unit three hydroxyl groups which can be reacted with theetherifying and/or alkylating reagents and/or further compounds, all ofwhich are known to the skilled worker, to form mixed cellulose ethersand/or substituted cellulose ethers.

The cellulose ethers are characterized conventionally using the terms DS(degree of substitution) and MS (degree of molar substitution), with DSgiving the average number of substituted hydroxyl groups in thecellulose per anhydroglucose unit and MS giving the average number ofmoles of the reactant combined with the cellulose/cellulose ether permole of anhydroglucose unit.

Examples of hydroxyl-containing cellulose ethers at least some of whosehydroxyl groups are substituted by ethylenically unsaturated radicalscan be found in a series of laid-open specifications, such as in DE-A-4015 158, DE-A-41 33 677, DE-A-197 51 712, and DE-A-197 08 531, forexample, which disclose cellulose ethers containing alkenyl groups, suchas cellulose ethers containing propenyl and butenyl groups, for example.

Particular preference is given to hydroxyl-containing cellulose ethershaving an MS of unsaturated radicals R_(unsaturated) of from 0.001 to1.0, preferably from 0.003 to 0.5, very preferably from 0.01 to 0.06,and more preferably still from 0.02 to 0.04.

The cellulose ethers may be synthesized for example frommethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose,dihydroxypropylcellulose, carboxymethylcellulose, the esters and saltsthereof with sodium, potassium, calcium, and ammonium ions,sulfoethylcellulose, methylhydroxyethylcellulose,methylhydroxypropylcellulose, methyl-dihydroxypropylcellulose,methylcarboxymethylcellulose, methylsulfoethyl-cellulose,ethylhydroxyethylcellulose, ethylhydroxypropylcellulose,ethyldihydroxypropylcellulose, ethylcarboxymethylcellulose,ethylsulfoethyl-cellulose, ethylhydroxyethylcellulose,dihydroxypropylcellulose, sulfoethyl-carboxymethylcellulose,dihydroxypropylsulfoethylcellulose, hydroxyethyl-sulfoethylcellulose,dihydroxypropylhydroxyethylcellulose,dihydroxypropyl-carboxymethylcellulose, andhydroxyethylcarboxymethylcellulose.

Suitable unsaturated radicals R_(unsaturated) include in principle allradicals which contain double bond systems and which can becopolymerized free-radically with the monomers (M). Thus, for example,R_(unsaturated) may be an alkenyl radical having more than 2 carbonatoms, such as propenyl or butenyl, for example. In addition it is alsopossible to use substituted mixed cellulose ethers where R_(unsaturated)is C(O)CR¹═CHR², C(O)CR³═CR⁴C(O)OR⁵, where R¹, R², R³, and R⁴═H or Meand R⁵═H, C₁-C₈ alkyl or sodium, potassium, or ammonium.

In one particularly preferred embodiment propenyl-substituted andbutenyl-substituted cellulose ethers of the hydroxyethylcellulose,hydroxypropylcellulose, dihydroxyethylcellulose, anddihydroxyethyl-hydroxyethylcellulose type having an MS_(propenyl) and/orbutenyl of from 0.001 to 1.0, preferably from 0.003 to 0.5, verypreferably from 0.01 to 0.06, and more preferably still from 0.02 to0.04 are used.

As hydroxyl-containing protective colloids at least some of whosehydroxyl groups are substituted by ethylenically unsaturated radicals itis preferred, in addition to the stated cellulose ethers, also to usepolyvinyl alcohols at least some of whose hydroxyl groups aresubstituted by ethylenically unsaturated radicals, as disclosed forexample in JP 1999/188,576.

It is also possible to use mixtures of two or more such protectivecolloids.

Alternatively use may also be made in addition of other protectivecolloids, such as the natural substances starch, gum arabic, alginatesor gum tragacanth, modified natural substances such as methyl-, ethyl-,hydroxyethyl- or carboxymethylcellulose, or starch modified by means ofsaturated acids or epoxides, and also synthetic substances such aspolyvinyl alcohol (with or without residual acetyl content) or partlyesterified or acetalized polyvinyl alcohol or polyvinyl alcoholetherified with saturated radicals, and also polypeptides, such asgelatin, and additionally polyvinylpyrrolidone, polyvinylmethylacetamideor poly(meth)acrylic acid.

The weight fraction of such additional, other protective colloids,present optionally, based on the total amount of the monomers used forthe preparation, is normally up to 15%.

Furthermore, in many cases it can be advantageous during the preparationof the dispersions to use, in addition to the protective colloids,nonionic and/or ionic emulsifiers, which may contribute to increasingthe latex stability, among other things.

Suitable nonionic emulsifiers are araliphatic and aliphatic nonionicemulsifiers, such as ethoxylated mono-, di-, and trialkylphenols (EOunits: 3 to 50, alkyl radical: C₄ to C₉), ethoxylates of long-chainalcohols (EO units: 3 to 50, alkyl radical: C₈ to C₃₆), and polyethyleneoxide/polypropylene oxide block copolymers, for example. Preference isgiven to ethoxylates of long-chain alkanols (alkyl radical: C₁₀ to C₂₂,average degree of ethoxylation: 3 to 50) and, of these, particularpreference to those based on naturally occurring alcohols, Guerbetalcohols or oxo alcohols having a linear or branched C₁₂-C₁₈ alkylradical and a degree of ethoxylation of from 8 to 50.

Further suitable emulsifiers can be found in Houben-Weyl, Methoden derorganischen Chemie, volume XIV/1, Makromolekulare Stoffe [Macromolecularcompounds], Georg-Thieme-Verlag, Stuttgart, 1961, pp. 192-208.

Suitable ionic emulsifiers include both anionic and cationicemulsifiers.

The anionic emulsifiers include alkali metal and ammonium salts of alkylsulfates (alkyl radical: C₈ to C₁₈), alkylphosphonates (alkyl radical:C₈ to C₁₈), of sulfuric monoesters or phosphoric monoesters and diesterswith ethoxylated alkanols (EO units: 2 to 50, alkyl radical: C₈ to C₂₂)and with ethoxylated alkylphenols (EO units: 3 to 50, alkyl radical: C₄to C₉), of alkylsulfonic acids (alkyl radical: C₁₂ to C₁₈), ofalkylarylsulfonic acids (alkyl radical: C₉ to C₁₈), of sulfosuccinicmonoesters and sulfosuccinic diesters of alkanols (alkyl radical: C₈ toC₂₂) and ethoxylated alkanols (EO units: 2 to 50, alkyl radical: C₈ toC₂₂), and of nonethoxylated and ethoxylated alkylphenols (EO units: 3 to50, alkyl radical: C₄ to C₉). In general the emulsifiers listed are usedin the form of technical-grade mixtures, with the figures for the lengthof alkyl radical and EO chain referring to the respective maximum of thedistributions occurring in the mixtures. Examples from the statedclasses of emulsifier are ®Texapon K12 (sodium lauryl sulfate fromCognis), ®Emulsogen EP (C₁₃-C₁₇ alkylsulfonate from Clariant), ®MaranilA 25 IS (sodium n-alkyl(C₁₀-C₁₃)benzenesulfonate from Cognis), ®Genapolliquid ZRO (sodium C₁₂/C₁₄ alkyl ether sulfate with 3 EO units fromClariant), ®Hostapal BVQ-4 (sodium salt of a nonylphenyl ether sulfatewith 4 EO units from Clariant), Aerosol MA 80 (sodiumdihexylsulfosuccinate from Cytec Industries), Aerosol A-268 (disodiumisodecylsulfosuccinate from Cytec Industries), and Aerosol A-103(disodium salt of a monoester of sulfosuccinic acid with an ethoxylatednonylphenyl from Cytec Industries).

Additionally suitable are compounds of the formula 1,

in which R¹ and R² are hydrogen or C₄-C₂₄ alkyl, preferably C₆-C₁₆alkyl, and are not simultaneously hydrogen, and X and Y are alkali metalions and/or ammonium ions. Frequently in the case of these emulsifiersuse is also made of technical-grade mixtures, which contain a fractionof from 50 to 90% by weight of the monoalkylated product, an examplebeing Dowfax® 2A1 (R¹═C₁₂ alkyl; DOW Chemical). The compounds aregeneral knowledge, from U.S. Pat. No. 4,269,749, for example, and areavailable commercially.

Additionally suitable as ionic emulsifiers are gemini surfactants, alsoknown to the skilled worker, as are described in, for example, the essay“Gemini-Tenside” by F. M. Menger and J. S. Keiper (Angew. Chem. 2000,pp. 1980-1996) and the publications cited therein.

The cationic emulsifiers include for example alkylammonium acetates(alkyl radical: C₈ to C₁₂), quaternary compounds containing ammoniumgroups, and pyridinium compounds.

Regarding the choice of ionic emulsifiers it must of course be ensuredthat incompatibilities in the resulting polymer dispersion, which canlead to coagulation, are ruled out. It is therefore preferred to useanionic emulsifiers in combination with anionic monomers or cationicemulsifiers in combination with cationic monomers, the combinations ofanionic emulsifiers and anionic monomers being particularly preferred.

Furthermore, it is possible to use both ionic and nonionic emulsifierswhich as an additional functionality include one or more unsaturateddouble bond units and which can be incorporated into the forming polymerchains during the polymerization process. These compounds, referred toas copolymerizable emulsifiers (“surfmers”), are general knowledge tothe skilled worker. Examples can be found in a series of publications(e.g.: “Reactive surfactants in heterophase polymerization” by A. Guyotet al. in Acta Polym. 1999, pp. 57-66) and are available commercially(e.g., ®Emulsogen R 208 from Clariant or Trem LF 40 from Cognis).

The amounts of the emulsifiers, where used, are within the usual limitsobserved. All in all, therefore, up to about 10% by weight, preferablyup to 5% by weight, based on the total amount of the monomers used forpreparing the dispersions, is used. Generally speaking, mixtures ofionic and nonionic emulsifiers are used, although it is also possible touse ionic and nonionic emulsifiers alone for additional stabilization ofthe dispersions.

Suitable free-radical polymerization initiators for starting andcontinuing the polymerization during the preparation of the dispersionsinclude all known initiators which are capable of starting afree-radical aqueous polymerization, preferably an emulsionpolymerization. They may be peroxides, such as alkali metalperoxodisulfates, for example, or azo compounds. As polymerizationinitiators it is also possible to use what are called redox initiators,which are composed of at least one organic and/or inorganic reducingagent and at least one peroxide and/or hydroperoxide, such as tert-butylhydroperoxide, for example, with sulfur compounds, such as the sodiumsalt of hydroxymethanesulfinic acid, sodium sulfite, sodium disulfite,sodium thiosulfate, and acetone-bisulfite adduct, for example, orhydrogen peroxide with ascorbic acid; as further reducing agents, whichmay form radicals with peroxides, it is also possible to use reducingsugars. Use may also be made of combined systems, which include a smallamount of a metal compound which is soluble in the polymerization mediumand whose metallic component is able to exist in a plurality of valencestates, such as ascorbic acid/iron (II) sulfate/hydrogen peroxide, forexample, in which ascorbic acid may frequently be replaced by the sodiumsalt of hydroxymethanesulfinic acid, acetone-bisulfite adduct, sodiumsulfite, sodium hydrogen sulfite or sodium bisulfite, and hydrogenperoxide by organic peroxides such as tert-butyl hydroperoxide or alkalimetal peroxodisulfates and/or ammonium peroxodisulfate, for example.Instead of said acetone-bisulfite adduct it is also possible to useother bisulfite adducts known to the skilled worker, such as thosedescribed, for example, in EP-A-0 778 290 and in the references citedtherein. Further preferred initiators are peroxodisulfates, such assodium peroxodisulfate, for example. The amount of the free-radicalinitiator systems used, based on the total amount of the monomers to bepolymerized, is preferably from 0.05 to 2.0% by weight.

The molecular weight of the homopolymers and/or copolymers of thedispersions can be adjusted by adding small amounts of one or moremolecular weight regulator substances. These regulators are usedgenerally in an amount of up to 2% by weight, based on the monomers tobe polymerized. As regulators it is possible to use all of thesubstances which are known to the skilled worker. Preference is given,for example, to organic thio compounds, silanes, allyl alcohols, andaldehydes.

The dispersion may further comprise a number of other substances, suchas plasticizers, preservatives, pH modifiers and/or defoamers, forexample.

The preparation of the aqueous polymer dispersions which are suitable inaccordance with the invention is not critical. Thus the emulsionpolymerization which is preferably carried out, or another method ofpolymerization, such as suspension or solution polymerization, can takeplace either batchwise or alternatively and preferably by semicontinuousprocesses. In the case of the semicontinuous processes the major amount,i.e., at least 70% by weight, preferably at least 90% by weight, of themonomers to be polymerized is supplied to the polymerization batchcontinuously, including by staged or gradient procedures. This procedureis also referred to as a monomer feed process, in which the term“monomer feed” refers to the metered addition of gaseous monomers,liquid monomer mixtures, monomer solutions or, in particular, aqueousmonomer emulsions. The individual monomers can be metered by means ofseparate feeds. In addition it is also possible, of course, to carry outthe metering of the monomers in a manner such that the mixture of themetered monomer compositions is varied in such a way that the resultingpolymer contains different polymer phases, something which ismanifested, for example, in the appearance of more than one glasstransition temperature when the dry polymer is analyzed by means ofdifferential scanning calorimetry.

In addition to the seed-free preparation mode it is also possible, inorder to set a defined polymer particle size, for the emulsionpolymerization to take place by the seed latex process or in thepresence of seed latices produced in situ. Such processes are known andare described at length in a multiplicity of patent applications (e.g.,EP-A-0 040 419 and EP-A-0 567 812) and publications (Encyclopedia ofPolymer Science and Technology, Vol. 5, John Wiley & Sons Inc., New York1966, p. 847).

Following the actual polymerization reaction it may be desirable and/ornecessary largely to free the aqueous polymer dispersions, suitable forthe purposes of the invention, from odorous substances, such as residualmonomers and other volatile organic constituents, for example. This canbe done in conventional manner physically, for example, by distillativeremoval (in particular by way of steam distillation) or by strippingwith an inert gas. The lowering of the residual monomer content can alsobe effected chemically by means of free-radical postpolymerization, inparticular by the action of redox initiator systems, as described forexample in DE-A-44 35 423. Preference is given to postpolymerizationwith a redox initiator system comprising at least one organic peroxideand an organic and/or inorganic sulfite. Particular preference is givento a combination of physical and chemical methods, in which case afterthe residual monomer content has been lowered by chemicalpostpolymerization it is lowered further by means of physical methods topreferably <1000 ppm, more preferably <500 ppm, in particular <100.

The further ingredients present if desired in the aqueous coatingcompositions of the invention with binder are guided by the particulardesired field of use.

The aqueous coating materials of the invention, with binder, can in factbe employed, for example, as primers, clear coating materials, adhesivesor else food coatings. In these cases these coating materials comprise,where appropriate, rheology-modifying additives and/or furthercomponents, such as defoamers, antislip additives, color pigments,antimicrobial preservatives, plasticizers, and film-forming auxiliaries,all of which are known to the skilled worker.

A further preferred embodiment of the present invention are pigmentedaqueous coating materials with binder.

These preferred pigmented coating materials, with particular preferenceemulsion paints, contain in general from 30 to 75% by weight, preferablyfrom 40 to 65% by weight, of nonvolatile constituents. These are allconstituents of the coating material with the exception of water, but atleast the total amount of solid binder, filler, pigment, andauxiliaries, such as plasticizers, rheology modifier, preservatives ordefoamers.

The nonvolatile constituents include preferably

-   a) from 3 to 90% by weight, more preferably from 10 to 60% by    weight, of the solids content of the at least one binder,-   b) from 5 to 85% by weight, more preferably from 10 to 60% by    weight, of at least one pigment,-   c) from 0 to 85% by weight, more preferably from 20 to 70% by    weight, of at least one filler, and-   d) from 0.05 to 40% by weight, more preferably from 0.5 to 15% by    weight, of customary auxiliaries.

Particular preference is given to solvent-free and plasticizer-freeaqueous coating materials.

The pigment volume concentration (PVC) of the pigmented aqueous coatingmaterials of the invention with binder is generally above 5%, preferablyin the range from 10 to 90%. In particularly preferred embodiments thePVCs are either in the range from 10 to 45% or in the range from 60 to90%, in particular from 70 to 90%.

As pigments it is possible to use any of the pigments known to theskilled worker for the stated end use. Preferred pigments for theaqueous coating materials of the invention with binder, preferably foremulsion paints, are titanium dioxide, preferably in the rutile form,barium sulfate, zinc oxide, zinc sulfide, basic lead carbonate, antimonytrioxide, and lithopones (zinc sulfide and barium sulfate), for example.It is, however, also possible for the aqueous formulations to includecolored pigments, examples being iron oxides, carbon black, graphite,luminescent pigments, zinc yellow, zinc green, ultramarine, manganeseblack, antimony black, manganese violet, Paris blue or Schweinfurtgreen. Besides the inorganic pigments, the formulations of the inventionmay also comprise organic color pigments, examples being sepia, gamboge,Cassel brown, toluidine red, Para red, Hansa yellow, indigo, azo dyes,anthraquinoid and indigoid dyes, and also dioxazine, quinacridone,phthalocyanine, isoindolinone, and metal complex pigments.

As fillers it is possible to use any of the fillers known to the skilledworker for the stated end use. Preferred fillers are aluminosilicates,such as feldspars, silicates, such as kaolin, talc, mica, and magnesite,alkaline earth metal carbonates, such as calcium carbonate, in the formfor example of calcite or chalk, magnesium carbonate, dolomite, alkalineearth metal sulfates, such as calcium sulfate, and silicon dioxide. Thefillers can be used either as individual components or as fillermixtures. Preference is given in the art to filler mixtures such ascalcium carbonate/kaolin and calcium carbonate/talc, for example.Synthetic-resin-bound plasters may also include relatively coarseaggregates, such as sands and sandstone granules.

In emulsion paints preference is generally given to finely dividedfillers. In order to increase the hiding power and to save on the use ofwhite pigments it is common in emulsion paints frequently to use finelydivided fillers, such as precipitated calcium carbonate or mixtures ofdifferent calcium carbonates with different particle sizes, for example.To adjust the hiding power, the shade, and the depth of color it ispreferred to use blends of color pigments and fillers.

The usual auxiliaries include wetting agents or dispersants, such assodium, potassium or ammonium polyphosphates, alkali metal salts andammonium salts of polyacrylic acids and of polymaleic acid,polyphosphonates, such as sodium 1-hydroxyethane-1,1-diphosphonate, andalso salts of naphthalenesulfonic acid, particularly the sodium saltsthereof. As dispersants it is additionally possible to use suitableamino alcohols, such as 2-amino-2-methylpropanol, for example. Thedispersants and wetting agents are used preferably in an amount of from0.1 to 2% by weight, based on the total weight of the emulsion paint.

The auxiliaries may further comprise thickeners, examples beingcellulose derivatives, such as methylcellulose, hydroxyethylcellulose,and carboxymethylcellulose, and also caseine, gum arabic, gumtragacanth, starch, sodium alginate, polyvinyl alcohol,polyvinylpyrrolidone, sodium polyacrylates, water-soluble copolymersbased on acrylic and (meth)acrylic acid, such as acrylic acid/acrylamidecopolymers and (meth)acrylic acid/acrylic ester copolymers, and what arecalled associative thickeners, such as styrene-maleic anhydride polymersor, preferably, the following, which are known to the skilled worker:hydrophobically modified polyether urethanes (HEUR), hydrophobicallymodified acrylic acid copolymers (HASE), and polyether polyols.

Inorganic thickeners as well, such as bentonites or hectorite, forexample, can be used.

The thickeners are used preferably in amounts of from 0.1 to 3% byweight, more preferably from 0.1 to 1% by weight, based on the totalweight of the aqueous coating material.

The aqueous coating materials of the invention may also comprisecrosslinking additives. Additives of this kind may be the following:aromatic ketones, such as alkyl phenyl ketones, which if desired haveone or more substituents on the phenyl ring, or benzophenone andsubstituted benzophenones as photoinitiators. Photoinitiators suitablefor this purpose are disclosed for example in DE-A-38 27 975 and EP-A-0417 568. Suitable compounds with a crosslinking action are alsowater-soluble compounds containing at least two amino groups, examplesbeing dihydrazides of aliphatic dicarboxylic acids, as disclosed forexample in DE-A-39 01 073, if monomers containing carbonyl groups havebeen copolymerized in the preparation of the aqueous polymer dispersionsuitable in accordance with the invention.

As auxiliaries in the aqueous coating compositions of the invention itis also possible, moreover, to use waxes based on paraffins andpolyethylene, and also dulling agents, defoamers, preservatives orhydrophobicizers, biocides, fibers, and further additives known to theskilled worker.

The pigmented aqueous coating materials of the invention may of coursealso comprise solvents and/or plasticizers as film-forming auxiliaries.Film-forming auxiliaries are general knowledge to the skilled worker andcan be used normally in amounts of from 0.1 to 20% by weight, based onthe solid binder present in the coating material, so that the aqueouscoating material has a minimum film-forming temperature of less than 15°C., preferably in the range from 0 to 10° C.

The present invention further provides the thixotropic coating materialsobtainable following the addition of a thixotropic agent, in particularof metal chelates, from the aqueous coating compositions of theinvention with binder.

Suitable metal chelates are the compounds normally used for thixotropingpurposes in aqueous emulsion paints, these compounds deriving primarilyfrom titanium and zirconium.

Suitable titanium chelates are the reaction products of isopropyl,n-butyl, and other low molecular weight ortho-esters of titanic acidwith one or more compounds from at least one of the following classes ofsubstance:

-   1. glycols containing at least two free hydroxyl groups, such as the    alkylene glycols 1,2-ethanediol (ethylene glycol), 1,2-propanediol,    1,3-propanediol, 1,2-butylene glycol, and 2-methyl-2,4-pentanediol;-   2. glycol ethers containing at least one free hydroxyl group, such    as the monoalkyl ethers of an alkylene glycol having up to 6 carbon    atoms. Examples of such glycol ethers are C₁-C₄ monoalkyl ethers of    ethylene glycol, diethylene glycol or of triethylene glycol, such as    2-methoxyethanol, 2-ethoxyethanol, 2-isopropoxyethanol and    2-n-butoxyethanol;-   3. alkanolamines, a class which embraces mono-, di-, and    trialkanolamines. Typical alkanolamines are monoethanolamine,    diethanolamine, triethanolamine, diisopropanolamine,    triisopropanol-amine, methyldiethanolamine,    β-aminoethylethanolamine, and 2-amino-2-ethyl-1,3-propanediol;-   4. alpha-hydroxy carboxylic acids, such as hydroxy monocarboxylic    acids and hydroxy dicarboxylic acids, which can contain one or more    hydroxyl groups per molecule, subject to the proviso that there is    at least one hydroxyl group positioned alpha to the carboxyl group,    such as lactic acid, glyoxylic acid, or tartaric acid, for example;-   5. beta-keto-carbonyl compounds, such as β-diketones and    β-keto-carboxylic acids. One compound from this class of substance    which is frequently used is acetylacetone, for example.

In general there is no need to isolate the reaction products in pureform; that is, the chelates formed can remain in solution in theliberated alcohol. Although the liberated alcohol can be separated offby distillation, the products obtained are in some cases of highviscosity and are therefore difficult to handle.

In many cases the titanium chelates are reaction products with only onecompound from only one of the stated classes of substance; thuswater-soluble titanium complexes of alpha-hydroxy acids and theirbarium, calcium, strontium or magnesium salts, and their preparation,are described in GB-A 811 524 and U.S. Pat. No. 2,453,520. In contrast,however, GB-A 2 207 434 also discloses titanium chelates which have aretarded gel effect and which are derived from the reaction of titanicacid with a combination of glycols/glycol ethers, alkanolamines, andα-hydroxy carboxylic acids.

Particular preference is given to the titanium chelates prepared fromthe reaction of titanic acid with alkanolamines. Examples of thesewidespread thixotropic agents are, among others, the commerciallyavailable products Vertec® AT23 and Vertec® AT33.

Suitable zirconium compounds are, for example, the thixotroping agentsprepared by reacting zirconyl carbonate with acetic acid, methacrylicacid or coconut oil fatty acid, and isopropanol, which are described inU.S. Pat. No. 3,280,050, for example.

Thixotroping agents of this kind can be added to the coating materialsof the invention in amounts between 0.05 and 5% by weight, preferablyfrom 0.1 to 2% by weight, based on the total amount of the coatingmaterial. The thixotroping agents can also, if desired, be added to anypigment pastes employed in the course of the preparation of pigmentedaqueous thixotropic coating materials, in which case they are addedimmediately prior to blending with the polymer dispersion.

The rheology aimed at in accordance with the invention for the aqueousthixotropic coating material, with or without pigment, is not usuallyestablished immediately after all of the ingredients necessary for thisproperty have been combined, but only over the course of a number ofhours, in some cases only after days, and is reinforced further in thecourse of storage. Generally speaking, 24 hours after the aqueousthixotropic coating material has been finished, thickening hasprogressed to a point where all of the target performance advantages arealready very much present, and the state in which there are no longerany substantial changes in rheology is attained after about 10 to 14days.

The aqueous coating materials of the invention are stable, fluid systemswhich can be used for coating and/or adhesively bonding a multiplicityof substrates. Consequently the present invention also relates tomethods of coating and/or adhesively bonding substrates and also to thecoating materials, including the adhesives, themselves. Examples ofsuitable substrates include wood, concrete, metal, glass, ceramics,plastics, plasters, wall coverings, paper, and painted, primed orweathered substrates. The application of the coating material to thetarget substrate takes place in a way which is dependent on the form ofthe coating material. Depending on the viscosity and the pigment contentof the coating material, and also on the substrate, application may takeplace by means of rollers, brushes, doctor blades or nozzles, or in theform of a spray.

The invention is described in more detail below, with reference toexamples, without being thereby restricted in any way whatsoever.

I. Preparation and Characterization of Dispersions

The vinyl acetate/ethylene dispersions prepared as part of the examplesare implemented in a 70 l pressure-rated autoclave with jacket coolingand a permissible pressure range of up to 160 bar. The preparation ofthe vinyl acetate/VeoVa10/butyl acrylate dispersions takes place in a 3l glass reactor. The parts and percentages used in the examples beloware by weight, unless noted otherwise.

The viscosity of the dispersions is determined using a Haake rotationalviscometer (Rheomat® VT 500) at room temperature with a shear gradientof 17.93 s⁻¹.

The mean particle size and the particle size distribution are determinedby laser and white light aerosol spectroscopy. The stated particle sizescorrespond to the particle diameter after drying.

The residual monomer amounts reported in the examples are determined bygas chromatography (GC).

The minimum film-forming temperature (MFFT) of the polymer dispersionsis determined on the basis of Ullmanns Enzyklopädie der technischenChemie, 4th ed. vol. 19, VCH Weinheim 1980, p. 17. The measuringapparatus used is what is called a film formation bar, and is composedof a metal plate to which a temperature gradient is applied and on whichtemperature sensors are mounted at various points for the purpose oftemperature calibration, the temperature gradient being chosen so thatone end of the film formation bar has a temperature above theanticipated MFFT and the other end has a temperature below theanticipated MFFT. The aqueous polymer dispersion is then applied to thefilm formation bar. In those regions of the film formation bar whosetemperature lies above the MFFT, a clear film is formed on drying, whilein the cooler regions cracks occur, and at lower temperatures still awhite powder is formed. On the basis of the known temperature profile ofthe plate the MFFT is determined visually as the temperature at whichthere is a crack-free film for the first time.

The glass transition temperature of the individual polymerization stagesis calculated in approximation by the Fox equation, taking into accountthe principal monomers. As a basis for the calculation the glasstransition temperatures of the homopolymers corresponding to theindividual monomers are used, these temperatures being described inUllmann's Encyclopedia of Industrial Chemistry, VCH Weinheim, vol. A 21(1992) p. 169 or in J. Brandrup, E. H. Immergut: Polymer Handbook 3rded., J. Wiley, New York 1989. For ethene a homopolymer glass transitiontemperature of 148 K is assumed (see J. Brandrup, E. H. Immergut:Polymer Handbook 3rd ed., J. Wiley, New York 1989, p. VI/214), for vinylacetate a homopolymer glass transition temperature of 315 K (seeUllmann's Encyclopedia of Industrial Chemistry, VCH Weinheim, vol. A 21(1992) p. 169), for vinyl versatate VeoVa®10 a homopolymer glasstransition temperature of 315 K (see Ullmann's Encyclopedia ofIndustrial Chemistry, VCH Weinheim, vol. A 21 (1992) p. 169), and forbutyl acrylate a homopolymer glass transition temperature of 315 K (seeUllmann's Encyclopedia of Industrial Chemistry, VCH Weinheim, vol. A 21(1992) p. 169).

I.1 Preparation of Vinyl Ester-Acrylic Ester Copolymer Dispersions UsingHydroxyethylcellulose

EXAMPLE A1

The monomer mixture used consists of 25% VeoVa®10 (vinyl ester ofα-branched C10 carboxylic acids, Shell), 67% vinyl acetate, and 8% butylacrylate. A 3-liter reactor with plane-ground joints and a lid ischarged with 992.9 g of deionized water and, with stirring and at roomtemperature, 11.7 g of hydroxyethylcellulose (Tylose H20, Clariant GmbH)are added and dissolved. Thereafter the following are added in order:

-   2.92 g sodium acetate-   175.2 g 20% strength solution of a nonylphenyl ethoxylate having 30    ethylene oxide units (®Arkopal N300, Clariant) in water-   116.8 g monomer mixture

The emulsion is heated to a temperature of 70° C. over the course of 30minutes, but when it reaches an internal temperature of 60° C. 51.4 g ofthe initiator solution I (10% strength sodium persulfate solution inwater) are added. After a 15-minute waiting time at 70° C. 1051.3 g ofmonomer mixture are fed in over the course of 180 minutes via a droppingfunnel.

After the end of monomer addition 24.5 g of the initiator solution 11(5% strength sodium persulfate solution in water) are added and stirringis continued at an internal temperature of 70° C. for 120 minutes.Subsequently the dispersion is cooled. The properties of the dispersionare summarized in table 1.

EXAMPLE A2

This dispersion is prepared as for example A1. Instead of 11.7 g ofTylose H20 23.4 g are used. The properties of the dispersion aresummarized in table 1.

EXAMPLE A3

This dispersion is prepared as for example A1. Instead of 11.7 g ofTylose H20 11.7 g of Tylose H200 (Clariant GmbH) are used. Theproperties of the dispersion are summarized in table 1.

EXAMPLE A4

This dispersion is prepared as for example A1. Instead of 11.7 g ofTylose H20 23.4 g of Tylose H200 (Clariant GmbH) are used. Theproperties of the dispersion are summarized in table 1.

I.2 Preparation of Vinyl Ester-Ethene Copolymer Dispersion UsingAllyl-Modified Hydroxyethylcellulose

EXAMPLE A5

This dispersion is prepared as for example A1. Instead of 11.7 g ofTylose H20 11.7 g of Tylose HL 40 AM (Clariant GmbH) are used. Theproperties of the dispersion are summarized in table 1.

I.3 Preparation of Vinyl Ester-Ethene Copolymer Dispersion UsingHydroxyethylcellulose

EXAMPLE A6

A 70 l pressure-rated reaction vessel with temperature regulator,stirrer mechanism, metering pumps, and metering means for gaseous ethene(mass through-flow measurement) is charged with a solution (initialcharge) consisting of the following constituents:  14825 g water  88.55g sodium acetate  594.5 g 30% strength sodium ethenesulfonate solutionin water  70.45 g sodium lauryl sulfate (® Texapon K12 granules, Cognis)  5284 g 20% strength solution of a nonylphenol ethoxylate having 30ethylene oxide units (® Arkopal N300, Clariant) in water  34.87 g  1%strength solution of Fe(II)-SO₄ × 7H₂O in water   7120 g  5% strengthsolution of the hydroxyethylcellulose Natrosol 250 GR (Hercules) inwater

The pH of the initial charge is 7.1. The apparatus is freed fromatmospheric oxygen by evacuating it twice and flushing with nitrogen.Evacuation is carried out a third time and then ethene is injected intothe apparatus until the internal pressure of the reactor is 30 bar.Subsequently 1586 g of vinyl acetate and 2.82 g of ®Rongalit C (BASF) insolution in 208 g of water are metered in. The internal temperature isthen raised to 60° C. When the internal temperature reaches 50° C. amixture of 4.0 g of an aqueous 70% strength tert-butyl hydroperoxidesolution and 208 g of water is metered in and cooling is carried out inorder to remove the heat of reaction. When the internal temperaturereaches 60° C. 30118 g of vinyl acetate, and also a solution of 25.4 gof ®Rongalit C in 2058 g of water and a mixture of 36.3 g of an aqueous70% strength tert-butyl hydroperoxide solution and 2058 g of water, aremetered in over the course of 360 minutes. The internal temperature isheld at 60° C. throughout the metering time. The ethene supply remainsopen at an internal pressure of 30 bar until a total of 3522 g of ethenehave been metered in. When all the metered additions are at an end asolution of 35.7 g of sodium peroxodisulfate in 832 g of water is added,the internal temperature is raised to 80° C., and when reaction is at anend, after a further hour, the mixture is cooled. The internal pressurein the reactor after cooling to 30° C. is 1.0 bar.

The properties of the dispersion are summarized in table 1.

EXAMPLE A7

The dispersion is prepared as for the preparation of the dispersiondescribed in example A6. In deviation therefrom the initial charge usedis a solution consisting of the following constituents (pH=6.7):   8060g water  88.55 g sodium acetate  594.5 g 30% strength sodiumethenesulfonate solution in water  70.45 g sodium lauryl sulfate(® Texapon K12 granules, Cognis)   5284 g 20% strength solution of anonylphenol ethoxylate having 30 ethylene oxide units (® Arkopal N300,Clariant) in water  34.87 g 1% strength solution of Fe(II)-SO₄ × 7H₂O inwater  14242 g 5% strength solution of the hydroxyethylcelluloseNatrosol 250 GR (Hercules) in water

The internal pressure of the reactor after cooling to 30° C. is 1.5 bar.

The properties of the dispersion are summarized in table 1.

EXAMPLE A8

The dispersion is prepared as for the preparation of the dispersiondescribed in example A6. In deviation therefrom the initial charge usedis a solution consisting of the following constituents (pH=7.1):  17343g water  88.55 g sodium acetate  594.5 g 30% strength sodiumethenesulfonate solution in water   2439 g 30% strength solution of asodium C₁₃-C₁₇ alkylsulfonate in water (® Emulsogen EP, Clariant)  34.87g 1% strength solution of Fe(II)-SO₄ × 7H₂O in water   7120 g 5%strength solution of the hydroxyethylcellulose Natrosol 250 GR(Hercules) in water

The internal pressure of the reactor after cooling to 30° C. is 0.7 bar.

The properties of the dispersion are summarized in table 1.

EXAMPLE A9

The dispersion is prepared as for the preparation of the dispersiondescribed in example A6. In deviation therefrom the initial charge usedis a solution consisting of the following constituents (pH=6.8):  10955g water  88.55 g sodium acetate  594.5 g 30% strength sodiumethenesulfonate solution in water   2439 g 30% strength solution of asodium C₁₃-C₁₇ alkylsulfonate in water (® Emulsogen EP, Clariant)  34.87g 1% strength solution of Fe(II)-SO₄ × 7H₂O in water  14240 g 5%strength solution of the hydroxyethylcellulose Natrosol 250 GR(Hercules) in water

The internal pressure of the reactor after cooling to 30° C. is 1.0 bar.

The properties of the dispersion are summarized in table 1.

EXAMPLE A10

Polymerization Stage 1:

A 70 l pressure-rated reaction vessel with temperature regulator,stirrer mechanism, metering pumps, and metering means for gaseous ethene(mass through-flow measurement) is charged with a solution (initialcharge) consisting of the following constituents:  14825 g water  88.55g sodium acetate  594.5 g 30% strength sodium ethenesulfonate solutionin water  70.45 g sodium lauryl sulfate (® Texapon K12 granules, Cognis)  5284 g 20% strength solution of a nonylphenol ethoxylate having 30ethylene oxide units (® Arkopal N300, Clariant) in water  34.87 g  1%strength solution of Fe(II)-SO₄ × 7H₂O in water   7120 g  5% strengthsolution of the hydroxyethylcellulose Natrosol 250 GR (Hercules) inwater

The pH of the initial charge is 6.9. The apparatus is freed fromatmospheric oxygen by evacuating it twice and flushing with nitrogen.Evacuation is carried out a third time and then a total of 350 g ofethene is injected into the apparatus; after this quantity of ethene hasbeen metered in, the internal pressure of the reactor is approximately 7bar. Subsequently the ethene supply is shut off and 3170 g of vinylacetate and 2.82 g of ®Rongalit C (BASF) in solution in 208 g of waterare metered in. Thereafter the internal temperature is raised to 60° C.When an internal temperature of 50° C. is reached a mixture of 4.0 g ofan aqueous 70% strength tert-butyl hydroperoxide solution and 208 g ofwater is metered in and cooling is carried out in order to remove theheat of reaction. When the internal temperature reaches 60° C. 7133 g ofvinyl acetate are metered in over 90 minutes and a solution of 9.1 g of®Rongalit C in 669 g of water and a mixture of 12.9 g of an aqueous 70%strength tert-butyl hydroperoxide solution and 669 g of water aremetered in over the course of 130 minutes. The internal temperature isheld at 60° C. throughout the metering time. A sample of dispersiontaken after the end of the metered additions of the initiator componentshas a residual vinyl acetate content <0.3% and a solids content of31.2%.

Polymerization Stage 2:

After the end of metering of the initiator solutions of the first stage,the ethene valve is opened and at an internal temperature of 60° C. theinternal pressure of the reactor is raised to 40 bar by metered additionof ethene. When the internal pressure of the reactor reaches 40 bar, atan internal temperature of 60° C., 21400 g of vinyl acetate, and also asolution of 18.8 g of ®Rongalit C in 1389 g of water and a mixture of27.0 g of an aqueous 70% strength tert-butyl hydroperoxide solution and1389 g of water, are metered in over the course of 270 minutes. Theethene supply remains open, at an internal pressure of 40 bar, until afurther 3172 g of ethene have been metered in. When all the meteredadditions are at an end a solution of 35.7 g of sodium peroxodisulfatein 832 g of water is added, the internal temperature is raised to 80°C., and after the end of reaction, after a further hour, the mixture iscooled. The internal pressure of the reactor after cooling to 30° C. is1.0 bar.

The properties of the dispersion are summarized in table 1.

EXAMPLE A11

The dispersion is prepared as for the preparation of the dispersiondescribed in example A10. In deviation therefrom the initial charge usedis a solution consisting of the following constituents (pH=6.9):   8060g water  88.55 g sodium acetate  594.5 g 30% strength sodiumethenesulfonate solution in water  70.45 g sodium lauryl sulfate(® Texapon K12 granules, Cognis)   5284 g 20% strength solution of anonylphenol ethoxylate having 30 ethylene oxide units (® Arkopal N300,Clariant) in water  34.87 g 1% strength solution of Fe(II)-SO₄ × 7H₂O inwater  14240 g 5% strength solution of the hydroxyethylcelluloseNatrosol 250 GR (Hercules) in water

The internal pressure of the reactor after cooling to 30° C. is 1.7 bar.

The properties of the dispersion are summarized in table 1.

EXAMPLE A12

The dispersion is prepared as for the preparation of the dispersiondescribed in example A10. In deviation therefrom the initial charge usedis a solution consisting of the following constituents (pH=6.9):  17343g water  88.55 g sodium acetate  594.5 g 30% strength sodiumethenesulfonate solution in water   2439 g 30% strength solution of asodium C₁₃-C₁₇ alkylsulfonate in water (® Emulsogen EP, Clariant)  34.87g 1% strength solution of Fe(II)-SO₄ × 7H₂O in water   7120 g 5%strength solution of the hydroxyethylcellulose Natrosol 250 GR(Hercules) in water

The internal pressure of the reactor after cooling to 30° C. is 1.0 bar.

The properties of the dispersion are summarized in table 1.

EXAMPLE A13

The dispersion is prepared as for the preparation of the dispersiondescribed in example A10. In deviation therefrom the initial charge usedis a solution consisting of the following constituents (pH=6.7):  10955g water  88.55 g sodium acetate  594.5 g 30% strength sodiumethenesulfonate solution in water   2439 g 30% strength solution of asodium C₁₃-C₁₇ alkylsulfonate in water (® Emulsogen EP, Clariant)  34.87g 1% strength solution of Fe(II)-SO₄ × 7H₂O in water  14240 g 5%strength solution of the hydroxyethylcellulose Natrosol 250 GR(Hercules) in water

The internal pressure of the reactor after cooling to 30° C. is 1.5 bar.

The properties of the dispersion are summarized in table 1.

I.4 Preparation of Vinyl Ester-Ethene Copolymer Dispersion UsingAllyl-Modified Hydroxyethylcellulose

EXAMPLE A14

The dispersion is prepared as for the preparation of the dispersiondescribed in example A6. In deviation therefrom the initial charge usedis a solution consisting of the following constituents (pH=7.1):  14825g water  88.55 g sodium acetate  594.5 g 30% strength sodiumethenesulfonate solution in water  70.45 g sodium lauryl sulfate(® Texapon K12 granules, Cognis)   5284 g 20% strength solution of anonylphenol ethoxylate having 30 ethylene oxide units (® Arkopal N300,Clariant) in water  34.87 g  1% strength solution of Fe(II)-SO₄ × 7H₂Oin water   7120 g  5% strength solution of the allyl-modifiedhydroxyethylcellulose Tylose HL 40 YG2 AM in water (Clariant GmbH)

The internal pressure of the reactor after cooling to 30° C. is 1.0 bar.

The properties of the dispersion are summarized in table 1.

EXAMPLE A15

The dispersion is prepared as for the preparation of the dispersiondescribed in example A6. In deviation therefrom the initial charge usedis a solution consisting of the following constituents (pH=7.2):  17343g water  88.55 g sodium acetate  594.5 g 30% strength sodiumethenesulfonate solution in water   2439 g 30% strength solution of asodium C₁₃-C₁₇ alkylsulfonate in water (® Emulsogen EP, Clariant)  34.87g 1% strength solution of Fe(II)-SO₄ × 7H₂O in water   7120 g 5%strength solution of the allyl-modified hydroxyethylcellulose Tylose HL40 YG2 AM in water (Clariant GmbH)

The internal pressure of the reactor after cooling to 30° C. is 0.8 bar.

The properties of the dispersion are summarized in table 1.

EXAMPLE A16

The dispersion is prepared as for the preparation of the dispersiondescribed in example A10. In deviation therefrom the initial charge usedis a solution consisting of the following constituents (pH=7.3): 14825 gwater 88.55 g sodium acetate 594.5 g 30% strength sodium ethenesulfonatesolution in water 70.45 g sodium lauryl sulfate (® Texapon K12 granules,Cognis) 5284 g 20% strength solution of a nonylphenol ethoxylate having30 ethylene oxide units (® Arkopal N300, Clariant) in water 34.87 g 1%strength solution of Fe(II)-SO₄ × 7H₂O in water 7120 g 5% strengthsolution of the allyl-modified hydroxyethyl- cellulose Tylose HL 40 YG2AM in water (Clariant GmbH)

The internal pressure of the reactor after cooling to 30° C. is 1.5 bar.

The properties of the dispersion are summarized in table 1.

EXAMPLE A17

The dispersion is prepared as for the preparation of the dispersiondescribed in example A10. In deviation therefrom the initial charge usedis a solution consisting of the following constituents (pH=7.3): 17343 gwater 88.55 g sodium acetate 594.5 g 30% strength sodium ethenesulfonatesolution in water 2439 g 30% strength solution of a sodium C₁₃-C₁₇alkylsulfonate in water (® Emulsogen EP, Clariant) 34.87 g 1% strengthsolution of Fe(II)-SO₄ × 7H₂O in water 7120 g 5% strength solution ofthe allyl-modified hydroxyethyl- cellulose Tylose HL 40 YG2 AM in water(Clariant GmbH)

The internal pressure of the reactor after cooling to 30° C. is 1.4 bar.

The properties of the dispersion are summarized in table 1. TABLE 1Dispersion properties Stabilizing system of the dispersion ProtectiveAmount Nonionic emulsifier Ionic emulsifier Viscosity Mean particleSolids MFFT Dispersion colloid^(a)) [pphm^(b))] [pphm^(b))] [pphm^(b))][mPas] diameter [nm] content [%] Tg [° C.] [° C.] A1 H20 1.0 3 0 255 21449.1 about 22 8 A2 H20 2.0 3 0 216 253 49.2 about 22 8 A3 H200 1.0 3 0295 248 49.3 about 22 8 A4 H200 2.0 3 0 110 302 49.9 about 22 8 A5 HL40AM 1.0 3 0 235 302 49.2 about 22 8 A6 250 GR 1.0 3 0.2 825 197 53.0about 10 4 A7 250 GR 2.0 3 0.2 1180 228 53.7 about 10 4 A14 HL40 AM 1.03 0.2 420 288 53.4 about 10 5 A8 250 GR 1.0 0 2.1 148 187 53.7 about 105 A9 250 GR 2.0 0 2.1 720 230 53.5 about 10 3 A15 HL40 AM 1.0 0 2.1 156277 52.7 about 10 5 A10 250 GR 1.0 3 0.2 822 190 53.4 about 2/31 5 A11250 GR 2.0 3 0.2 1120 226 53.7 about 2/31 3 A16 HL40 AM 1.0 3 0.2 614291 53.6 about 2/31 3 A12 250 GR 1.0 0 2.1 143 220 53.5 about 2/31 4 A13250 GR 2.0 0 2.1 534 248 53.7 about 2/31 5 A17 HL40 AM 1.0 0 2.1 280 25453.0 about 2/31 4

-   a) hydroxyethylcelluloses: H20=Tylose H20, Clariant GmbH,    H200=Tylose H200, Clariant GmbH; HL 40 AM=Tylose HL 40 AM,    allyl-modified hydroxyethylcellulose from Clariant GmbH; 250    GR=Natrosol 250 GR, Hercules-   b) pphm =amounts used in parts by weight per 100 parts by weight of    monomer.    II. Preparation of Emulsion Paints    II.1 Preparation of Solventborne Gloss Paints

EXAMPLES B1 TO B5

Solventborne gloss paints are formulated from the aqueous polymerdispersions A1 to A5. This is done by initially introducing thefollowing constituents into a vessel: 92.5 g water 0.5 ghydroxyethylcellulose rheological assistant having a viscosity of 30mPas (determined as a 1.9% strength solution in water at 25° C.);Tylose ® H 20 YG4; Clariant 4.0 g 10% strength by weight solution of asodium polyphosphate in water, Calgon ®; BK Giulini Chemie GmbH & Co,OHG 3.0 g dispersing aid Mowiplus XW 330, Clariant 3.0 g defoamerAgitan ® 310; Münzing-Chemie GmbH, Heilbronn 3.0 g sodium hydroxidesolution (10%) 2.0 g preservative Mergal ® K 9 N; Troy Chemie GmbH,Seelze

The following is added with stirring: 175.0 g titanium dioxide pigmentKronos ® 2065; Kronos Titan GmbH, Leverkusen

The constituents are mixed for 20 minutes in a high-speed disperser.Subsequently the following constituents are added with stirring: 724.7 gpolymer dispersion A (49.0% by weight) 37.0 g 1,2-propanediol 10.0 gbutyl diglycol acetate

The pigment volume concentration (PVC) of the solventborne gloss paintis about 11.9%; the gloss paints of examples B1 to B5 were preparedusing the dispersions A1 to A5 indicated in the following table: ExampleB1^(a)) B2^(a)) B3^(a)) B4^(a)) B5^(b)) Dispersion A1 A2 A3 A4 A5^(a))comparative example;^(b))inventive example

The thixotroping properties of the gloss paints B1 to B5 are summarizedin table 2 (see below: section 111.1).

II.2 Preparation of Solvent-Free and Plasticizer-Free Interior Paints

Solvent-free and plasticizer-free interior paints are formulated fromaqueous polymer dispersions A6 to A17. This is done by initiallyintroducing the following constituents into a vessel: 315.0 g water 6.0g hydroxyethylcellulose rheological assistant having a viscosity of 300mPas (determined as a 1.9% strength solution in water at 25° C.);Tylose ® H 300 YG4; Clariant 10.0 g 10% strength by weight solution of asodium polyphosphate in water, Calgon ®; BK Giulini Chemie GmbH & Co,OHG 5.0 g dispersing aid Mowiplus XW 330, Clariant 3.0 g defoamerAgitan ® 310; Münzing-Chemie GmbH, Heilbronn 3.0 g sodium hydroxidesolution (10%) 2.0 g preservative Mergal ® K 9 N; Troy Chemie GmbH,Seelze

The following is added with stirring: 250.0 g titanium dioxide pigmentKronos ® 2065; Kronos Titan GmbH, Leverkusen 156.0 g calcium carbonate,calcite 5 μm - calcite mean particle size 5 μm; Omyacarb 5 GU; OmyaGmbH, Cologne

The constituents are mixed for 20 minutes in a high-speed disperser.Subsequently the following constituents are added with stirring: 238.7 gpolymer dispersion A (53.0% by weight)

The pigment volume concentration (PVC) of the solvent-free andplasticizer-free interior paints is about 50.3%; the interior paints ofexamples B6 to B17 were prepared using the dispersions A6 to A17indicated in the following table: Example B6^(a)) B7^(a)) B8^(b))B9^(a)) B10^(a)) B11^(b)) B12^(a)) B13^(a)) B14^(b)) B15^(a)) B16^(a))B17^(b)) Dispersion A6 A7 A14 A8 A9 A15 A10 A11 A16 A12 A13 A17^(a))comparative example;^(b))inventive example

The thixotroping properties of these interior paints are summarized intable 3 (see below: section III.).

III. Preparation of Thixotropic Coating Compositions:

III.1 Thixotroping of Emulsion Paints

The emulsion paints described in examples B1-B17 were thixotroped byadding, with slow stirring (1000 rpm), an appropriate amount of heavymetal chelate Tilcom AT 23 (triethanolamine titanate from TitaniumIntermediates Ltd., London) diluted with water in a 1:1 ratio.

24 hours after the addition of the heavy metal chelate the gel strengthis measured in an ICI gel strength tester (ICI Rotothinner for paints,Sheen Instruments Ltd., Sheendale Road, Richmond, Surrey, England,serial number 771331). The thixotroping was performed in each case atthe percentage by weight indicated in the tables below, based on thetotal weight of the emulsion paint. In all cases it was possible toeliminate the gel structure by means of severe sheering stress, and onsubsequent standing the gel structure was largely reestablished in theprevious gel strength. TABLE 2 Thixotroping behavior of the gloss paintsfrom examples B1 to B5 Stabilization of the dispersion A present in thegloss paint B Nonionic Protective Amount emulsifier Ionic emulsifier Gelstrength Tilcom AT 23 addition^(e)) Example Gloss paint colloid^(c))[pphm^(d))] [pphm^(d))] [pphm^(d))] 0.3% by weight 0.5% by weight 0.7%by weight C1a^(a)) B1^(a)) H20 1.0 3 0 0 C1b^(a)) 6 C1c^(a)) 15 C2a^(a))B2^(a)) H20 2.0 3 0 13 C2b^(a)) 34 C2c^(a)) 63 C3a^(a)) B3^(a)) H200 1.03 0 4 C3b^(a)) 11 C3c^(a)) 31 C4a^(a)) B4^(a)) H200 2.0 3 0 12 C4b^(a))45 C4c^(a)) 90 C5a^(b)) B5^(b)) HL40 AM 1.0 3 0 55 C5b^(b)) 139 C5c^(b))214^(a))Comparative example;^(b))inventive example;^(c))hydroxyethylcelluloses: H20 = Tylose H20, Clariant GmbH, H200 =Tylose H200, Clariant GmbH; HL 40 AM = Tylose HL 40 AM, allyl-modifiedhydroxyethylcellulose from Clariant GmbH;^(d))pphm = amount used in parts by weight per 100 parts by weight ofmonomer;^(e))amount added based on total mass of emulsion paint B.

TABLE 3 Thixotroping behavior of the interior paints from examples B6 toB11 (single-stage dispersions) Stabilization of the dispersion A(single-stage dispersions) present in the gloss paint B NonionicProtective Amount emulsifier Ionic emulsifier Gel strength after TilcomAT 23 addition^(e)) Example Gloss paint colloid^(c)) [pphm^(d))][pphm^(d))] [pphm^(d))] 0.5% by weight 0.75% by weight 1.0% by weightC6a^(a)) B6 250 GR 1.0 3 0.2 16 C6b^(a)) 33 C6c^(a)) 78 C7a^(a)) B7 250GR 2.0 22 C7b^(a)) 53 C7c^(a)) 102 C8a^(b)) B8 HL40 AM 1.0 61 C8b^(b))108 C8c^(b)) 202 C9a^(a)) B9 250 GR 1.0 0 2.1 12 C9b^(a)) 32 C9c^(a)) 63C10a^(a)) B10 250 GR 2.0 27 C10b^(a)) 62 C10c^(a)) 113 C11a^(a)) B11HL40 AM 1.0 98 C11b^(a)) 146 C11c^(a)) 225^(a))Comparative example;^(b))inventive example;^(c))hydroxyethylcelluloses: 250 GR = Natrosol 250 GR, Hercules, HL 40AM = Tylose HL 40 AM, allyl-modified hydroxyethylcellulose from ClariantGmbH;^(d))pphm = amount used in parts by weight per 100 parts by weight ofmonomer;^(e))amount added based on total mass of emulsion paint B.

TABLE 4 Thixotroping behavior of the interior paints from examples B12to B17 (two-stage dispersions) Stabilization of the dispersion A(single-stage dispersions) present in the gloss paint B ProtectiveNonionic emulsifier Ionic emulsifier Gel strength after Tilcom AT 23addition^(e)) Example Gloss paint colloid^(c)) Amount [pphm^(d))][pphm^(d))] [pphm^(d))] 0.5% by weight 0.75% by weight 1.0% by weightC12a^(a)) B12 250 GR 1.0 3 0.2 17 C12b^(a)) 39 C12c^(a)) 82 C13a^(a))B13 250 GR 2.0 32 C13b^(a)) 63 C13c^(a)) 125 C14a^(b)) B14 AL H40 AM 1.072 C14b^(b)) 132 C14c^(b)) 217 C15a^(a)) B15 250 GR 1.0 0 2.1 12C15b^(a)) 37 C15c^(a)) 73 C16a^(a)) B16 250 GR 2.0 29 C16b^(a)) 59C16c^(a)) 107 C17a^(b)) B17 HL40 AM 1.0 104 C17b^(b)) 154 C17c^(b)) 232^(a))Comparative example;^(b))inventive example;^(c))hydroxyethylcelluloses: H20 = Tylose H20, Clariant GmbH, H200 =Tylose H200, Clariant GmbH; HL 40 AM = Tylose HL 40 AM, allyl-modifiedhydroxyethylcellulose from Clariant GmbH;^(d))pphm = amount used in parts by weight per 100 parts by weight ofmonomer;^(e))amount added based on total mass of emulsion paint B.

The gel strengths listed in tables 2-4 depend heavily on the compositionof the dispersions used for preparing the emulsion paints B1-B17, and soare comparable with one another only where the dispersions are of thesame kind.

Comparison of examples C1-C5 illustrates that the inventive aqueouscoating composition B5 is distinguished over the comparison paints B1-B4by drastically improved thixotropic properties. Thus the inventive glosspaint B5, with either the same or even with a lower added amount oftitanium chelate, exhibits a significantly higher thixotropability (gelstrength) (compare examples C5b and C5c versus C1c, C2c, C3c, and C4c).This applies in particular to gloss paints B2 and. B4 as well, whichwere formulated with dispersions whose preparation took place in thepresence of twice the amount of hydroxyl-containing protective colloid(C5 versus C2 and C4). From comparison of examples C1, C3, and C5 it canbe inferred that the high gel strength in the case of the inventivethixotropic gloss paints C5 is not attributable to different molecularweights of the hydroxyl-containing protective colloids used forpreparing the dispersion (C5c versus C1c and C3c, and C5b versus C1b andC3b, and C5a versus C1a and C3a) but instead is based on the use of adispersion which comprises an ethylenically unsaturatedhydroxyl-containing protective colloid.

The interior paint examples C6-C17 underline the fact that the effectaccording to the invention not only occurs independently of theemulsifier system in the dispersions used to prepare the interior paints(compare in each case C6-C8, C9-C11, C12-C14, and C15-C17) but is alsoindependent of whether the dispersions were prepared by a single-stageor multistage polymerization process.

1-20. (canceled)
 21. An aqueous coating material with binder, comprisingat least one aqueous polymer dispersion based on a homopolymer,copolymer, or combination thereof derived from (α,β-unsaturatedcompounds (m), said aqueous polymer dispersion further comprising atleast one hydroxyl-containing protective colloid having ethylenicallyunsaturated radicals.
 22. A coating material as claimed in claim 21,wherein the homopolymer, copolymer, or combinations thereof are derivedfrom principal monomers (MP) which are selected from the groupconsisting of vinyl esters of carboxylic acids having 1 to 18 carbonatoms (MP1), monoesters of ethylenically unsaturated C₃-C₈monocarboxylic and dicarboxylic acids with C₁-C₁₈ alkanols (MP2),aromatic or aliphatic (α,β-unsaturated, optionally halogen-substitutedhydrocarbons (MP3), and functional monomers (MF) selected from the groupconsisting of ionic monomers (MF1), nonionic monomers (MF2),ethylenically unsaturated monomers (MF3), or a combination thereof. 23.A coating material as claimed in claim 21, wherein the homopolymer,copolymer, or combination thereof is derived from monomer mixturesselected from the group consisting of vinyl acetate/vinylchloride/ethene, vinyl acetate/vinyl laurate/ethene, vinyl acetate/vinyllaurate/ethene/vinyl chloride, vinyl acetate/Versatic acid vinylester/ethene/vinyl chloride, Versatic acid vinyl ester/ethene/vinylchloride, vinyl acetate/Versatic acid vinyl ester/ethene, vinylacetate/ethene, vinyl acetate/butyl acrylate, vinyl acetate/dibutylmaleate, vinyl acetate/dibutyl fumarate, vinyl acetate/2-ethylhexylacrylate, vinyl acetate/ethene/butyl acrylate, vinylacetate/ethene/dibutyl maleate, vinyl acetate/ethene/dibutyl fumarate,vinyl acetate/ethene/2-ethylhexyl acrylate, methyl methacrylate/butylacrylate, methyl methacrylate/2-ethylhexyl acrylate, styrene/butylacrylate, styrene/2-ethylhexyl acrylate, methyl methacrylate/isobutylacrylate, or methyl methacrylate/isopropyl acrylate.
 24. A coatingmaterial as claimed in claim 22, wherein the homopolymer, copolymer, orcombination thereof is derived from monomer mixtures selected from thegroup consisting of vinyl acetate/vinyl chloride/ethene, vinylacetate/vinyl laurate/ethene, vinyl acetate/vinyl laurate/ethene/vinylchloride, vinyl acetate/Versatic acid vinyl ester/ethene/vinyl chloride,Versatic acid vinyl ester/ethene/vinyl chloride, vinyl acetate/Versaticacid vinyl ester/ethene, vinyl acetate/ethene, vinyl acetate/butylacrylate, vinyl acetate/dibutyl maleate, vinyl acetate/dibutyl fumarate,vinyl acetate/2-ethylhexyl acrylate, vinyl acetate/ethene/butylacrylate, vinyl acetate/ethene/dibutyl maleate, vinylacetate/ethene/dibutyl fumarate, vinyl acetate/ethene/2-ethylhexylacrylate, methyl methacrylate/butyl acrylate, methylmethacrylate/2-ethylhexyl acrylate, styrene/butyl acrylate,styrene/2-ethylhexyl acrylate, methyl methacrylate/isobutyl acrylate, ormethyl methacrylate/isopropyl acrylate.
 25. A coating material asclaimed in claim 21, wherein the amount of hydroxyl-containingprotective colloid having ethylenically unsaturated radicals is 0.05-25%by weight, based on the total mass of the monomers used to prepare thedispersion.
 26. A coating material as claimed in claim 21, wherein theamount of hydroxyl-containing protective colloid having ethylenicallyunsaturated radicals is 0.4-5% by weight, based on the total mass of themonomers used to prepare the dispersion.
 27. A coating material asclaimed in claim 21 wherein said hydroxyl-containing protective colloidcomprises cellulose ethers.
 28. A coating material as claimed in claim27 wherein said cellulose ethers have an MS of unsaturated radicals(R_(unsturated)) in the range of from 0.001 to 1.0.
 29. A coatingmaterial as claimed in claim 27 wherein said cellulose ethers have an MSof unsaturated radicals (R_(unsturated)) in range of from 0.02 to 0.04.30. A coating material as claimed in claim 21, wherein saidhydroxyl-containing protective colloids are cellulose ethers synthesizedfrom cellulose selected from the group consisting of methylcellulose,hydroxyethylcellulose, hydroxypropylcellulose, dihydroxypropylcellulose,carboxymethylcellulose, sulfoethylcellulose,methylhydroxyethylcellulose, methylhydroxypropylcellulose,methyldihydroxypropylcellulose, methylcarboxymethylcellulose,methylsulfoethylcellulose, ethylhydroxyethylcellulose,ethylhydroxypropylcellulose, ethyldihydroxypropylcellulose,ethylcarboxymethylcellulose, ethylsulfoethylcellulose,ethylhydroxyethylcellulose, dihydroxypropylcellulose,sulfoethylcarboxymethylcellulose, dihydroxypropylsulfoethylcellulose,hydroxyethylsulfoethylcellulose, dihydroxypropylhydroxyethylcellulose,dihydroxypropylcarboxymethylcellulosehydroxyethylcarboxymethylcellulose, and the esters and salts thereof.31. A coating material as claimed in claim 27, wherein said celluloseethers are synthesized from cellulose selected from the group consistingof methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose,dihydroxypropylcellulose, carboxymethylcellulose, sulfoethylcellulose,methylhydroxyethylcellulose, methylhydroxypropylcellulose,methyldihydroxypropylcellulose, methylcarboxymethylcellulose,methylsulfoethylcellulose, ethylhydroxyethylcellulose,ethylhydroxypropylcellulose, ethyldihydroxypropylcellulose,ethylcarboxymethylcellulose, ethylsulfoethylcellulose,ethylhydroxyethylcellulose, dihydroxypropylcellulose,sulfoethylcarboxymethylcellulose, dihydroxypropylsulfoethylcellulose,hydroxyethylsulfoethylcellulose, dihydroxypropylhydroxyethylcellulose,dihydroxypropylcarboxymethylcellulosehydroxyethylcarboxymethylcellulose, and the esters and salts thereof.32. A coating material as claimed in claim 21 wherein thehydroxyl-containing protective colloids comprise unsaturated radicals,R_(unsaturated), containing double bond systems, where R_(unsaturated)is an alkenyl radical having more than 2 carbon atoms, C(O)CR¹═CHR² orC(O)CR³═CR⁴C(O)OR⁵, wherein R¹, R², R³, and R⁴ is H or Me and R⁵═H,C₁-C₈ alkyl, sodium, potassium, or ammonium.
 33. A coating material asclaimed in claim 30 wherein the hydroxyl-containing protective colloidscomprise unsaturated radicals, R_(unsaturated), containing double bondsystems, where R_(unsaturated) is an alkenyl radical having more than 2carbon atoms, C(O)CR¹═CHR² or C(O)CR³═CR⁴C(O)OR⁵, wherein R¹, R², R³,and R⁴ is H or Me and R⁵═H, C₁-C₈ alkyl, sodium, potassium, or ammonium.34. A coating material as claimed in claim 21, wherein saidhydroxyl-containing protective colloids are propenyl-substituted andbutenyl-substituted cellulose ethers of hydroxyethylcellulose,hydroxypropylcellulose, dihydroxyethylcellulose, anddihydroxyethyl-hydroxyethylcellulose having anMS_(propenyl and/or butenyl) of from 0.001 to 1.0.
 35. A coatingmaterial as claimed in claim 32, wherein said hydroxyl-containingprotective colloids are propenyl-substituted and butenyl-substitutedcellulose ethers of hydroxyethylcellulose, hydroxypropylcellulose,dihydroxyethylcellulose, and dihydroxyethyl-hydroxyethylcellulose havingan MS_(propenyl and/or butenyl) of from 0.02 to 0.04.
 36. A coatingmaterial as claimed in claim 21 wherein said hydroxyl-containingprotective colloids are polyvinyl alcohols having at least one hydroxylgroup substituted by ethylenically unsaturated radicals.
 37. A coatingmaterial as claimed in claim 25 wherein said hydroxyl-containingprotective colloids are polyvinyl alcohols having at least one hydroxylgroup substituted by ethylenically unsaturated radicals.
 38. A coatingmaterial as claimed in claim 21 further comprising, in addition to thehydroxyl-containing protective colloids, a second protective colloidselected from the group consisting of natural substances, modifiednatural substances, and synthetic substances.
 39. A coating material asclaimed in claim 36 further comprising, in addition to thehydroxyl-containing protective colloids, a second protective colloidselected from the group consisting of natural substances, modifiednatural substances, and synthetic substances.
 40. A coating material asclaimed in claim 21 further comprising at least one pigment.
 41. Acoating material as claimed in claim 38 further comprising at least onepigment.
 42. A coating material as claimed in claim 40, comprisingwater, binders, fillers, pigments, and auxiliaries.
 43. A coatingmaterial as claimed in claim 21 further comprising at least onethixotroping agent.
 44. A coating material as claimed in claim 42further comprising at least one thixotroping agent.
 45. A coatingmaterial as claimed in claim 43 wherein said thixotroping agent has atleast one metal chelate.
 46. A coating material as claimed in claim 45,wherein said metal chelate contains titanium, zirconium, or acombination thereof.
 47. A coating material as claimed in claim 36,wherein said metal chelates are the reaction products of isopropyl,n-butyl, low molecular weight ortho-esters of titanic acid, or acombination thereof with one or more compounds selected from the groupconsisting of glycols containing at least two free hydroxyl groups,glycol ethers containing at least one free hydroxyl group, mono, di, ortri alkanolamines, alpha-hydroxy carboxylic acids, which can optionallycontain one or more hydroxyl groups per molecule, with the proviso thatthere is at least one hydroxyl group positioned alpha to the carboxylgroup, and beta-keto-carbonyl compounds.
 48. A coating material asclaimed in claim 45, wherein the metal chelates are present in amountsin the range from 0.05 to 5% by weight, based on the total amount of thecoating material.
 49. A coating material as claimed in claim 48 whereinthe metal chelates are present in amounts in the range from 0.1 to 2% byweight based on the total amount of the coating material.
 50. A processfor preparing a coating material as claimed in claim 21 wherein at leastone α,β-unsaturated compound (M) is polymerized in an emulsion by asemicontinuous process, wherein at least 70% by weight of the monomersto be polymerized are supplied continuously by a stage or a gradientprocedure to the polymerization batch.
 51. The process of claim 50wherein at least 90% of the monomers to be polymerized are suppliedcontinuously by a stage or a gradient procedure to the polymerizationbatch.
 52. The process as claimed in claim 50, wherein the metering ofthe individual monomers takes place by means of separate feeds orwherein the metering of the monomers is carried out such that themixture of the metered monomer compositions is varied such that theresulting polymer has different polymer phases.
 53. A process forpreparing a coating material as claimed in claim 21 wherein at least oneα,β-unsaturated compound (M) is polymerized batchwise in an emulsion.